The photosynthesis is the process used by plants and bacteria cells to convert inorganic matter in organic thanks to the light energy. This process consist on several steps, being one of them the electronic transport from the photosystem II to the cytochrome thanks to plastoquinone-9 (PQ). Here we prepare membranes that mimic the characteristics and composition of natural photosynthetic cell membranes and we characterize them in order to obtain the PQ molecules position in the membrane and their electrochemical behaviour. The selected galactolipid is digalactosyldiacylglycerol (DGDG) that represents the 30% of the thylakoid membrane lipid content. The results obtained are worthful for several science fields due to the relevance of galactolipids as anti-algal, anti-viral, anti-tumor and anti-inflammatory agents and the antioxidant and free radical scavenger properties of prenylquinones.; Both pure components (DGDG and PQ) and the DGDG:PQ mixtures have been studied using surface pressure-area isotherms. These isotherms give information about the film stability and indicate the thermodynamic behaviour of the mixture and their physical state. The Langmuir-Blodgett (LB) film has been transferred forming a monolayer that mimics the bottom layer of the biological membranes. This monolayer on mica has been topo-graphically characterized using AFM and both the height and the physical state that they present have been obtained. Moreover, these monolayers have been transferred onto ITO that is a hydrophilic substrate with good optical and electrical features, so that, it is suitable for studying the electrochemical behaviour of these systems and it is a good candidate for energy producing devices. (C) 2015 Elsevier B.V. All rights reserved.

Photosynthetic organisms use light to convert the inorganic matter in organic one. Photosynthetic process consists on several steps, and one of them involves plastoquinone (PQ) that acts as electron and proton shuttle between photosystem II and cytochrome. We prepared membranes that mimic the characteristics and composition of natural photosynthetic membranes and we characterized them using several techniques in order to obtain both the PQ molecules disposition in the membrane and their electrochemical behavior. The selected lipid was monogalactosyldiacylglycerol (MGDG) that represents the 50% of the lipid content of the thylakoid membrane. Both MGDG and PQ, and the MGDG:PQ mixtures have been studied using surface pressure–area isotherms and the presence of PQ alters the physical state and compactness of the MGDG matrix. Langmuir–Blodgett (LB) films have been obtained by transferring a monolayer that mimics half of the bilayer of a biological membrane. The AFM topographical characterization of the monolayers on mica indicates the presence of differentiated domains, corresponding to different physical states linked to the influence of the PQ content. Moreover, the electrochemical behavior of the monolayers has been studied when transferred on ITO, observing one main electrochemical process that is due to the diving position of PQ molecules in the lipid matrix

The objective of this work is to apply Atomic Force Microscopy in Peak Force mode to obtain topographic characteristics (mean roughness, root-mean-square roughness, skewness and kurtosis) and mechanical characteristics (adhesion, elastic modulus) of Siloxane-Hydrogel Soft Contact Lenses (CLs) of two different materials, Lotrafilcon B of Air Optix (AO) and Asmofilcon A of PremiO (P), after use (worn CLs). Thus, the results obtained with both materials will be compared, as well as the changes produced by the wear at a nanoscopic level. The results show significant changes in the topographic and mechanical characteristics of the CLs, at a nanoscopic level, due to wear. The AO CL show values of the topographic parameters lower than those of the P CL after wear, which correlates with a better comfort qualification given to the former by the wearers. A significant correlation has also been obtained between the adhesion values found after the use of the CLs with tear quality tests, both break-up-time and Schirmer. (C) 2015 Elsevier B.V. All rights reserved.

Contact lenses (CLs) are of common use and the biocompatibility, topography and mechanical properties of the used materials are of major importance. The objective of this contribution is to apply the AFM in mode Peak Force to obtain surface topography and mechanical characteristics of un-worn CLs of different materials. One material of hydrogel, two of siloxane-hydrogel and one of rigid gas-permeable were used in the study. The results obtained with different materials have been compared, at a nanoscopic level, and the conclusions are diverse. There is no significant influence of the two environments used to measure the characteristics of the CLs, either water or saline solution. The pHEMA hydrogel CL (Polymacon of Soflens) shows the highest values of roughness, adhesion and elastic modulus. The siloxane-hydrogel CL named Asmofilcon A of PremiO presents the lowest values of mean roughness (R-a), root-mean-square roughness (RMS or R-q), adhesion (Adh) and elastic modulus (Y-m), meanwhile the siloxane-hydrogel CL named Lotrafilcon B of Air Optix presents the lowest value of skewness (R-sk) and the rigid gas-permeable CL, named RXD, presents the lowest values of kurtosis (R-ku) and maximum roughness (R-max).

In this work we report the fabrication of Langmuir and Langmuir-Blodgett (LB) films of a substituted ZnPc (octakis(oxyoctyl) phthalocyanine of zinc), and their characterization by means of several techniques. These characterization techniques include surface pressure (pi-A) and surface potential (Delta V-A) isotherms as well as UV-vis Reflection spectroscopy and Brewster Angle Microscopy (BAM) for the films at the air-water interface together with UV-vis absorption and IR spectroscopies and Atomic Force Microscopy (AFM) for the LB films. The pi-A and Delta V-A isotherms and BAM images indicate a phase transition at a surface pressure of ca. 9mN/m and a multilayer formation at surface pressures around 19-20 mN/ m; at a surface pressure around 27 mN/ m a disordered collapse of the film occurs. In addition, AFM images of LB films at p= 10mN/ mand p= 20 mN/ m show a monomolecular and a multilayered film, respectively. The comparison of the UV-vis spectrum of ZnPc in solution, the reflection spectra of the Langmuir films and UV-vis spectra of LB films reveals a significant reduction in the Q band intensity for the films, indicative of an organization of ZnPc in the Langmuir and LB films versus the randomdistribution in solution. The UV-vis Reflection spectra are also consistentwith multilayer formation at surface pressures around 19-20 mN/ m. The relative intensities of the IR spectrum bands change from the KBr pellet to the LB filmwhich is also attributable to orientation effects in the film. Cyclic voltammetric experiments of LB films incorporating the ZnPc derivative show peaks that can be correlated with redox processes occurring in the phthalocyanine ring. A small but significant influence of the surface pressure and the number of deposited layers in the electrochemical behaviour is observed. The electrochemical response of cast films exhibits some differences with respect to that of LB films which have been attributed to their different molecular organizations. (C) 2014 Elsevier B. V. All rights reserved.

Bacterial-mediated diseases are a major healthcare concern worldwide due to the rapid spread of antibiotic-resistant bacteria. One strategy to manage the bacterial infections while avoiding the emergence of resistant strains implies specific targeting and disruption of bacteria membranes. This work evaluates the potential of nanostructured biopolymer derivatives, nanocapsules (NCs), to disrupt the bacteria cell walls and effectively kill planktonic microorganisms. Two biopolymers, chitosan and cellulose, were chemically modified to synthesize derivatives with improved cationic character (thiolated chitosan and aminocellulose) prior to their processing into nanocapsules via a one-step sonochemical process. The interactions of NCs, displaying an average size of around 250 nm, with bacteria membrane were evaluated using two membrane models: Langmuir monolayers and liposome bilayers composed of a l-a-phosphatidylglycerol phospholipid extracted from Escherichia coli. NCs possessed improved membrane disturbing capacity in comparison to the nonprocessed biopolymer derivatives, by drastically increasing the monolayer fluidity and inducing more than 50% leakage of a dye inserted in the bilayered liposomes. In addition, membrane disturbance was directly proportional to the NCs cationic charge. Whereas evidence showed that thiolated chitosan and aminocellulose interacted with the bacteria membrane through a “carpet model”, the NCs were found to induce larger surface defects and high local perturbance through a “detergent model”. Importantly, the degree of disruption caused by the biopolymer derivatives and NCs correlated well with the antimicrobial capacity against Escherichia coli, selectively killing bacteria cells without imparting toxicity to human fibroblasts.

Ubiquinone (UQ) is one of the main electron and proton shuttle molecules in biological systems, and dipalmitoylphosphatidylcholine (DPPC) is one of the most used model lipids. Supported planar bilayers (SPBs) are extensively accepted as biological model membranes. In this study, SPBs have been deposited on ITO, which is a semiconductor with good electrical and optical features. Specifically, topographic atomic force microscopy (AFM) images and force curves have been performed on SPBs with several DPPC:UQ ratios to study the location and the interaction of UQ in the SPB. Additionally, cyclic voltammetry has been used to understand the electrochemical behavior of DPPC:UQ SPBs. Obtained results show that, in our case, UQ is placed in two main different positions in SPBs. First, between the DPPC hydrophobic chains, fact that originates a decrease in the breakthrough force of the bilayer, and the second between the two leaflets that form the SPBs. This second position occurs when increasing the UQ content, fact that eventually forms UQ aggregates at high concentrations. The formation of aggregates produces an expansion of the SPB average height and a bimodal distribution of the breakthrough force. The voltammetric response of UQ depends on its position on the bilayer.

Ubiquinone (UQ) is one of the main electron
and proton shuttle molecules in biological systems, and
dipalmitoylphosphatidylcholine (DPPC) is one of the most
used model lipids. Supported planar bilayers (SPBs) are
extensively accepted as biological model membranes. In this
study, SPBs have been deposited on ITO, which is a
semiconductor with good electrical and optical features.
Speci
fi
cally, topographic atomic force microscopy (AFM)
images and force curves have been performed on SPBs with
several DPPC:UQ ratios to study the location and the
interaction of UQ in the SPB. Additionally, cyclic voltammetry
has been used to understand the electrochemical behavior of
DPPC:UQ SPBs. Obtained results show that, in our case, UQ
is placed in two main di
ff
erent positions in SPBs. First,
between the DPPC hydrophobic chains, fact that originates a
decrease in the breakthrough force of the bilayer, and the
second between the two lea
fl
ets that form the SPBs. This
second position occurs when increasing the UQ content, fact
that eventually forms UQ aggregates at high concentrations.
The formation of aggregates produces an expansion of the SPB
average height and a bimodal distribution of the breakthrough
force. The voltammetric response of UQ depends on its
position on the bilayer

Ubiquinone (UQ) is one of the main electron and proton shuttle molecules in biological systems, and dipalmitoylphosphatidylcholine (DPPC) is one of the most used model lipids. Supported planar bilayers (SPBs) are extensively accepted as biological model membranes. In this study, SPBs have been deposited on ITO, which is a semiconductor with good electrical and optical features. Specifically, topographic atomic force microscopy (AFM) images and force curves have been performed on SPBs with several DPPC:UQ ratios to study the location and the interaction of UQ in the SPB. Additionally, cyclic voltammetry has been used to understand the electrochemical behavior of DPPC:UQ SPBs. Obtained results show that, in our case, UQ is placed in two main different positions in SPBs. First, between the DPPC hydrophobic chains, fact that originates a decrease in the breakthrough force of the bilayer, and the second between the two leaflets that form the SPBs. This second position occurs when increasing the UQ content, fact that eventually forms UQ aggregates at high concentrations. The formation of aggregates produces an expansion of the SPB average height and a bimodal distribution of the breakthrough force. The voltammetric response of UQ depends on its position on the bilayer.

Nanoparticles possess unique physicochemical properties, important for the efficient transport through the cell membranes. The small and controllable size, large surface area to mass ratio, and high reactivity facilitate the intracellular delivery, thereby overcoming some of the limitations in traditional antimicrobial therapeutics. Chemically modified biopolymers (thiolated chitosan and aminocellulose) were processed into nanoparticles via a one-step sonochemical process and evaluated for their antibacterial activity against Escherichia coli and Staphyloccocus aureus. Thiolated chitosan and aminocellulose were shown to possess improved antimicrobial properties compared to the starting biopolymers and even higher bactericide effect was observed after processed into nanoparticles. The mechanistic insights were obtained by Langmuir monolayer technique using Escherichia coli phospholipids as membrane models. The high cationic character of the modified biopolymers and the obtained spherical structure were found to allow efficient interaction with the phospholipid heads and tails, crucial for their antibacterial activity and transport through cell membranes.

Rhodopsin is the photoreceptor located in the rod cells of the retina. It has seven transmembrane helices and is a prototypic member of the G protein-coupled receptor superfamily. The structures and functions of these receptors are clearly affected by the lipid composition of the cell membrane, and their study in a purified recombinant form is usually performed in detergent solution. There is a need to study these receptors in a physiologically relevant environment because the lipid environment is known to have an important effect on their function. In this work, rhodopsin reconstituted in docosahexaenoic acid (DHA) liposomes is shown to have more thermal stability than when it is solubilised with the neutral detergent dodecyl maltoside. Moreover, the specific interaction between rhodopsin and DHA was followed by means of Langmuir experiments with insertion of rhodopsin into lipid monolayers; this showed high affinity for the lipid-receptor interaction...

Ubiquinone and plastoquinone are two of the main electron and proton shuttle molecules in biological systems, and monogalactosyldiacylglycerol (MGDG) is the most abundant lipid in the thylakoid membrane of chloroplasts. Saturated MGDG, ubiquinone-10 (UQ) and MGDG:UQ mixed monolayers at the air/water interface have been studied using surface pressure–area isotherms and Brewster Angle Microscopy. Moreover, the transferred Langmuir–Blodgett films have been observed by Atomic Force Microscopy. The results show that MGDG:UQ mixtures present more fluid phase than pure MGDG, indicating a higher order degree for the later. It is also observed an important influence of UQ on the MGDG matrix before UQ collapse pressure and a low influence after this event, due to UQ expulsion from the MGDG matrix. This expulsion leads to a similar remaining UQ content for all the tested mixtures, indicating a limiting content of this molecule in the MGDG matrix at high surface pressures. The thermodynamic studies confirm the stability of the MGDG:UQ mixtures at low surface pressures, although presenting a non-ideal behaviour. Results point to consider UQ as a good candidate for studies of artificial photosynthesis.

The structure and the electrochemical behaviour of Langmuir and Langmuir–Blodgett (LB) films of the biological ubiquinone-10 (UQ) and a mixture of dipalmytoilphosphatidylcholine (DPPC) and UQ at the molar ratios DPPC:UQ 5:1 and 10:1 have been investigated. The surface pressure-area isotherms of the Langmuir films and the AFM images of the LB films show the formation of a monolayer in the DPPC:UQ mixture till a certain surface pressure is attained, and then at higher surface pressures the UQ is progressively expelled. The cyclic voltammograms of DPPC:UQ LB films formed on indium tin oxide, ITO, at different surface pressures show one reduction and one oxidation peak at low surface pressures, but two or even more reduction and oxidations peaks at medium and high surface pressures. The electrochemical behaviour is correlated with the film structure.